Alkali metal derivatives of alkanols in gasoline fuels



United States Patent Ofiic 3,367,759 Patented Feb. 6, 1968 ABSTRACT OF THE DISCLOSURE Alkali metal oxides of hydroxy ethers and hydrocarbon solutions thereof.

This invention relates to novel alkali metal derivatives of alkanols and to useful hydrocarbon compositions containing them. More particularly, the invention is concerned with a new class of alkali metal oxides of certain alcohols and phenols having improved solubility in hydrocarbons.

Alkali metal oxides, i.e. alkoxides and phenoxides, are generally infusible compounds having very low solubilities in hydrocarbons. They are strongly basic and thus useful in chemical reactions requiring a strong base having an organic radical as part of the molecule. The low solubilities of these compounds in hydrocarbons limit their utility in reactions carried out in hydrocarbon solvents since the insoluble powdered alkali alkoxide or phenoxide reacts very slowly.

It has been found that a new class of alkali metal derivatives of alcohols and phenols is provided in the alkali metal oxides of hydroxy ethers selected from the group consisting of monohydrocarbyl ethers of 1,2-glycols, 1,3-glycols, 1,2-dihydroxybenzenes and o-hydroxybenzyl alcohols, said glycols, hydroxybenzenes, alcohols and hydrocarbyl groups each containing from 2. to carbon atoms.

The metal derivatives of the ether-hydroxy organic compounds of the invention can be prepared by reacting an alkali metal or a hydride of an alkali metal with the ether-alcohol or ether-phenol. This is usually carried out by contacting the metal or hydride with the ether-alcohol or phenol in a hydrocarbon solvent to prepare a solution of the alkali metal derivative or ether alcoholate as it may be formed. The alkali metals include lithium, sodium, potassium, rubidium and cesium, with the first three preferred for availability and effectiveness.

As stated earlier, the organic hydroxy compounds yielding alkali metal oxides (or salts, considering alcohol as a weak acid) soluble in hydrocarbons must be monohydrocarbyl ethers of dihydroxy compounds having the hydroxy groups in the 1,2- or 1,3-positions. The nature of the hydrocarbyl radical forming the ether with one of the hydroxyl groups is not too critical, and it may be acyclic, alicyclic or aromatic in nature. Examples of ethers of 1,2-glycols which are effective are the octyl, phenyl and cyclohexyl monoethers of the ethylene glycol, isobutylene glycol, 1,2-hexylene glycol or phenylethylene glycol. Examples of ethers of 1,3-glycols are the monoethyl ether of 1,3-propanediol and the 3-ethyl ether of 1,3- butanediol. The n-amyl ether of pyrocatechol is an example of a monoether of 1,2-dihydroxybenzene. An example of a monoether of o-hydroxybenzyl alcohol is 2- methoxybenzyl alcohol.

For present purposes the glycol or hydroxy aryl portion of the monoethers of the present invention is preferably an alkylene glycol of 2 to 4 carbon atoms as in the case of ethylene glycol, etc., or a dihydroxy aryl hydrocarbon of 6 to 10 carbon atoms as in the case of 1,2-dihydroxy benzene, o-hydroxybenzyl etc.

The monoethers of the foregoing type are characterized by the general formula in which R is 1,2-alkylene or 1,3-alkylene of 2 to 4 carbon atoms, cycloalkylene, arylene or arylalkylene of 6 to 10 carbon atoms and R is alkyl of 2 to 4 carbon atoms or cycloalkyl, aryl or arylalkyl of 6 to 10 carbon atoms.

The nature of the hydrocarbon used as a solvent is not critical and may be parafiin, naphthene, olefin, aromatic or mixtures of these. It may be quite volatile such as pentane, or high boiling such as a lubricating oil fraction. Mixtures of hydrocarbons such as gasoline fractions are often preferred. For many purposes, it is desirable to prepare a concentrated solution of the metaloxy-compound in a hydrocarbon such as pentane and to use this concentrated solution as ail-additive in other hydrocarbon systems.

The alkali metal ether alcoholates of the invention are soluble in hydrocarbon over a considerable range of proportions. Generally, amounts of from about 0.1 to about 10% by Weight are suitable from the standpoint of stable solutions. Concentrates, however, may contain as high as about 20% because of the unusual degree of solubility of the alkali metal ether alcoholates.

The metaloxy-compounds of the invention are useful antiknock agents in gasoline. They are also useful as hydrocarbon-soluble bases for catalysts and for preparing alkali metal salts in hydrocarbon systems. These salts thus prepared or the metaloxy-bases themselves are useful lubricating oil additives, especially for use in engines employing high sulfur fuels which give rise to sulfuric acid during combustion.

The following examples are offered as further illustration of the alkali metal derivatives of alkanols and their preparation in accordance with the present invention. Unless otherwise specified the proportions are on a Weight basis.

Example 1.Lithium "salt of methoxyelhanol A solution of 7.1 g. (0.093 mole) of methoxyethanol in 250 g. of pentane was prepared. To this was added 0.64 g. (0.093 mole) of lithium, and the mixture was stirred overnight after which time the metal was dissolved. This solution of the lithium salt of methoxyethanol had a concentration of 1.9 g./ ml. of pentane.

Example 2.-S0dium salt of methoxyethanol The procedure of the previous example was followed using 22.6 g. (0.3 mole) of methoxyethanol and an excess of sodium hydride in 350 ml. of dry pentane. When the reaction was complete, the solution was filtered to yield the sodium salt. The concentration was 8.3 g./ 100 ml. of pentane.

Example 3.-Ptassium salt 0 melhoxyetltanol phenol in 390 eg. (420 ml.) of benzene was added 1.04 (0.15 mole) of lithium metal. After stirring overnight,

the lithium was dissolved yielding a clear solution containing 4.6 g. of salt/100 ml. of benzene.

,- The effectiveness of the alkali metal derivatives of alkanols as antiknock additives in gasoline was evaluated in a series of tests. In the tests the commonly accepted Using the same procedure as in the previous examples, 4.2 g. (0.108 mole) of potassium metal was reacted with 8.2 g. (0.108 mole) of methoxyethanol in 250 g. of pentane. The potassium dissolved completely to yield a solution containing 3.1 g. of the salt/l00 ml. of pentane.

Example 4' sodimn Salt of l'methoxy'z'methyl' F-l research method octane numbers and F-2 motor Z-propmzol method octane numbers were obtained on various sodium Toa solution of 18 g. (0.17 mole) of l methoxy-2- and lithium ether oxides in a variety of base fuels. The methyl-2-propanol in 350 ml. of dry pentane was added test results are set out in the following table:

TABLE.ANTIKNOCK PROPERTIES OF ALKALI METAL DERIVATIVES Octane Numbers Example Additive, Compound No. Base Fuel Description Wt. Base Fuel Test Fuel percent F-l F-2 F-l F-l F-2 F-2 Lithium 2-meth0xyethoxide 1 11% n-pentane, 89% isooctaneu O. 4 94. 0 94. 2 95. 2 +1 2 96. 7 +2 5 Sodium Z-methoxyethoxide. 2 11% n-pentane, 89% isooctane. 0. 4 94. 0 94. 2 98. 3 +4 3 98. 2 +4 0 Lithium 2-methoxyphenate. .1. 9 11% benzene, 89% isooctane 0. 6 100.8 98. 4 103. 4 +2 6 99.0 +0 6 excess sodium hydride. After the evolution of hydrogen 5 The above test results show that the lithium and sodium had stopped, the pentane solution was filtered yielding a salts impart definite octane number improvements to clear light yellow solution. This solution contained 6.2 g. high octane base fuels. of salt/ 100 ml. of pentane. As illustrated by the foregoing examples, the present invention also relates to improved gasoline fuels containing the alkali metal derivatives of alkanols as antiknock agents. The base fuels are typical hydrocarbons Example 5.S0dium salt of t-lzutoxy-Z- methyl-Z-propanol To a solution of 10 g. of t-butoxy-2-methyl-2-pr0pa110 boiling in the gasoline boiling range suitable for use in in 350 ml. of dry pentane was added an excess of sodium spark ignition type engines. They are conveniently prehydride. After completion of the reaction, the excess pared by the usual refining and blending process and hydride was removed by filtration yielding a clear solu normally contain straight-chain parafiins, branch-chain tion of the salt which had a concentration of 3.3 g./ 100 parafiins, olefins, aromatics and naphthenes. The unml. of pentane. leaded base fuel is generally characterized with having an ASTM (D-86) distillation with an initial boiling point Example 6-Prepawli0n f yof about 90 F. and a final boiling point of about 425 F. P P 40 Such base fuels have a clear Research octane number of about 85 to about 100 as determined by the accepted This compound was prepared in order to form its CPR engine test method htlmlm In a 1 flask equlpped Wlth a The alkali metal derivative of alkanol may be used st1rrer, condenser, and additlon funnel was added 90 g. as the Sole antiknock agent in the gasoline or it may be Sodlum hydroxlde In 1500 mefhanoL To thls used in combination with organolead antiknock additives mlxture was added 130 Of l=3dlc hlorolsoprf)panol and such as tetramethyl lead, tetraethyl lead, ethyltrimethyl 100 g. of dry methanol. The solution was stirred for 1 lead tetrapropyl lead, tetraphenyl lead, vinyltrimethyl hour while refluxing. The sodium chloride formed in the lead em remftion removed by filtration "W the solution was The alkali metal derivative is used in amounts sufiicient distilled to y1eld 40 g. of product boillng at 84 C. under to improve the octane numben Ordinarily amounts in a Pressure of 34 mm of the range of from 0.1 to 2.0% by weight are suitable for this purpose.

While the character of this invention has been described in detail with numerous examples, this has been done by way of illustration only and without limitation of the invention. It will be apparent to those skilled in the art that numerous modifications and variations of the illustrative examples may be made in the practice of the invention within the scope of the following claims.

Example 7.Lithium "salts of 1,3-

dimethoxy-Z-propanol To a solution of 6.0 g. (0.05 mole) of 1,3-dimethoxy-2- propanol in 300 g. of pentane was added 500 mg. (0.063 mole) of lithium hydride. The mixture was stirred overnight, and the solution was filtered. This yielded a pentane solution containing 1.3 g. of salt/ 100 ml. This same experiment was repeated using benzene in place of pentane i sg g Oxides of h drox th h a th to yield a benzene solution containing 1.8 g./ 100 ml. of forr'nula y y e as e SOlVent.

Example 8.-Sodium salt of 1,3-dimeth0xyin which R is selected from the group consisting of 1,2-

2-pr0pan0l alkylene and 1,3-alkylene groups of 2 to 4 carbon atoms,

To a Solution of 6.0 g. (005 mole) of 1,} dimethomh cycloalkylene, arylene and arylalkylene groups of 6 to 10 carbon atoms, and R is selected from the group consisting of alkyl of 2 to 4 carbon atoms, cycloalkyl, aryl and arylalkyl groups of 6 to 10 carbon atoms, said alkali 7 metal oxides being soluble in hydrocarbon solvents.

2. Improved gasoline fuels containing the alkali metal oxide of claim 1 in an amount sufficient to improve the Example 9.--Lillziunz salt 0/ o-mellzoxyphenol Octane number- 2-propanol in 210 g. of pentane was added 2.4 g. (0.05 mole) of sodium hydride (50% pure). The solution was stirred until the reaction was complete and filtered. The clear solution had a concentration of 2.5 g. of salt/l00 ml. of pentane.

To a solution of 18.6 g. (0.15 mole) of omethoxy- (Referemes on f fl i page) 5 6 References Cited 2,796,443 6/1957 Mey er et a1. 260-615 ig 2,151,432 3/1939 Lyons et a1. 44 77 PATRICK P. GARVIN, Przmefry Examzner. 2,184,956 12/1939 Gilliland et a1. 44-77 5 DANIEL WYMAN, Exammer- 2,716,057 8/1955 Whaley 260-615 C. F. DEES, Assistant Examiner. 

